Use of derivatives of methylene-bis-oxazolidine and compositions obtained thereby

ABSTRACT

The present invention relates to stable microbicidal compositions which are characterized in that they comprise derivatives of methylenebisoxazolidine and 1H-benzimidazol-2-ylcarbamic acid. The compositions according to the invention can be employed in industrial products. The derivatives of methylenebisoxazolidine are used, in particular, for increasing the solubility of derivatives of 1H-benzimidazol-2-ylcarbamic acid in liquid preparations.

This application is a division of Ser. No. 09/391,649 filed Sep. 8, 1999now U.S. Pat. No. 6,348,483.

FIELD OF THE INVENTION

The present invention relates to the use of methylenebisoxazolidinederivatives for increasing the solubility of derivatives of1H-benzimidazol-2-ylcarbamic acid in liquid preparations orpreservatives for use in industrial products.

Methyl 1H-benzimidazol-2-ylcarbamate (carbendazim) is known in the priorart as a fungicide. The active compound has no bactericidal action andis virtually insoluble in water and in most organic solvents. Thus, onlyvia salt formation, for example using strong acids such as HCl, H₂SO₄,Malon AS 3 acid (4-C₁₀₋₁₃-sec-alkyl derivative of benzenesulphonicacid), is it possible to improve the solubility of carbendazim inpreparations to such an extent that use in liquid concentrates, forexample, is possible. However, in some cases salt formation requires aconsiderable reaction expense. Thus, for example for preparingcarbendasulf (salt of carbendazim and mono-C₁₀₋₁₄-alkylbenzenesulphonicacid) requires heating carbendazim with Malon AS 3 acid in propyleneglycol for 4 hours. Moreover, by-products are formed in this reaction,resulting in losses of activity. Although the concentration ofcarbendazim in the liquid concentrates described is below 4% by weight,precipitation frequently occurs after some time. Carbendazim andcarbendasulf are virtually insoluble in aqueous systems.

Aqueous dispersions based on carbendazim, such as the commercial productParmetol DF 19 Forte (aqueous dispersion based on carbendazim(fungicide) and diuron (1,1-dimethyl-3-(3,4-dichlorophenyl)urea)(algicide)) are known. However, such preparations are not water-soluble.Stable carbendasulf-comprising concentrates having a limited content ofcarbendasulf (for example the commercial product Parmetol DF 18) arelikewise known from the prior art. However, they have an unsatifactorystability towards low temperatures, and they do not form any clearsolutions in water.

Hitherto, the preparation of an aqueous preparation comprisingcarbendazim or carbendasulf as fungicidal active compound did not seemto be possible or economical.

Derivatives of methylenebisoxazolidine, such as3,3′-methylenebis-(5-methyloxazolidine) (trade name: Mar 71) are used aswater-soluble bactericides; however, in practice they frequently onlyhave low fungicidal activity.

Liquid preparations of Mar 71 and the fungicide Kathon 893 (preparationof N-octylisothiazolone in 1,2-propylene glycol), for example, areknown. However, these products are not sufficiently stable towardsalkali, and in particular the fungicide decomposes at a pH above about9.5 and is furthermore subject to degradation by nucleophilic agents.

OBJECT OF THE INVENTION

It was therefore an object of the present invention to increase thesolubility of derivatives of 1H-benzimidazol-2-ylcarbamic acid in liquidpreparations and to provide compositions which, in addition to goodfungicidal or algicidal activity, also have satisfactory bactericidaland, if appropriate, virucidal activity. With a view to possibleapplications in cooling lubricants (concentrates and emulsions), in thefungicidal, algicidal, bactericidal and/or virucidal finishing ofproducts or coatings such as paints, renders and sealing materials, thesubstances used should have satisfactory stability towards alkali.

SUMMARY OF THE INVENTION

This object is achieved by using derivatives of methylenebisoxazolidineto increase the solubility of derivatives of1H-benzimidazol-2-ylcarbamic acid in liquid preparations.

The invention accordingly also provides stable microbicidal compositionswhich are characterized in that they comprise derivatives ofmethylenebisoxazolidine and 1H-benzimidazol-2-ylcarbamic acid. Here,microbicidal compositions are to be understood as meaning algicidal,bactericidal, fungicidal and/or virucidal compositions.

The present invention furthermore provides the use of such compositions.

Preferred embodiments are the subject of the subclaims.

Surprisingly, it has been found that homogeneous clear solutions ofderivatives of 1H-benzimidazol-2-ylcarbamic acid (carbendazim) can beprepared in the presence of derivatives of methylenebisoxazolidine.

Furthermore, it has been found that by using derivatives ofmethylenebisoxazolidine and, if appropriate, other active compounds,additives and/or auxiliaries, it is possible to obtain clear homogeneousconcentrates whose content of carbendazim can be above 10% by weight.

These concentrates can be employed to prepare, by dilution with water,ready-to-use solutions which are likewise clear and homogeneous. Inaddition to good bactericidal action, these ready-to-use dilutions haveexcellent fungicidal and algicidal action and/or virucidal activity.

Advantageously, the odour and the emission of formaldehyde of theresulting preparations are simultaneously, in particular at highcontents of carbendazim, strongly reduced.

The preparations furthermore have, by comparison, excellent stabilitytowards alkali and low temperatures. Moreover, they have a sufficientlyhigh buffer capacity to maintain an alkaline medium.

The emission of formaldehyde or formaldehyde depot compounds from thesepreparations according to the invention is considerably lower than thatof the preparations based on the individual components, for example Mar71. Furthermore, the use according to the invention ofmethylenebisoxazolidine together with carbendazim results in synergisticaction.

The compositions according to the invention generally have a pH of up to12, in particular up to 11 and preferably up to 10.

For preparing the compositions according to the invention, use ispreferably made of 3,3′-methylenebis-(5-methyloxazolidine) (trade nameMar 71).

Preferred carbamic acid derivatives are selected from methyl1H-benzimidazol-2-ylcarbamate or its salts, for example themonohydrochloride, the monohydrobromide or the salt of Malon AS 3 acid,and methyl 1-(butylcarbamoyl)benzimidazol-2-ylcarbamate.

The compositions may comprise further active compounds, in particularN-formals and/or O-formals, additives and/or auxiliaries. It is possibleto add, for example, the following substances:

further microbicidally active compounds, such as N-formals (for exampleGrotan BK, alpha, alpha′,alpha″-trimethyl-1,3,5-triazine-1,3,5-(2H,4H,6H)-triethanol,4,4-dimethyloxazolidine, dimethylolurea, 5-ethyl-3,7-dioxa-1-azabicyclo[3.3.0] octane, 2-(hydroxymethylamino) ethanol,methylenebistetrahydro-1,3-bisoxazine, N-methylolchloroacetamide,bis(hydroxymethyl)-5,5-dimethylhydantoin, diazolidinylurea,Na-hydroxymethylglycinate, 3,4,4-trimethyloxazolidine), O-formals (forexample propylene glycol hemiformal, propylene glycol bishemiformal,ethylene glycol bishemiformal, benzyl alcohol hemiformal, butyl diglycolhemiformal), heterocycles (for example 1,2-benzisothiazolin-3-one,5-chloro-2-methylisothiazolin-3-one, 2-methylisothiazolin-3-one,N-octylisothiazolin-3-one, 2-mercaptopyridine N-oxide or its salts, suchas Na or zinc salt, pyrion disulphide, thiabenzazole,N-cyclohexylbenzo(b)thiophene-2-carboxamide 1,1-dioxide), halogenatedorganic compounds (for example 3-iodopropinyl butylcarbamate,2-bromo-2-nitropropane-1,3-diol, dibromodicyanobutane)

other active compounds, such as N-cyclohexyl-N-nitrosohydroxylamine orits salts, such as Na, K or Al salts

algicides, such as diuron (1,1-dimethyl-3-(3,4-dichlorophenyl)urea),Irgarol 1051(2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine),terbutryn (2-methylthio-4-tert-butylamino-6-ethylamino-s-triazine)

insecticides, acaricides, nematocides

substances for regulating or adjusting the pH (for example amines oralkanolamines, in particular primary and tertiary amines oralkanolamines, acids, carboxylic acids, salts, buffers)

odour-masking substances, odour modifiers, perfume

colorants

additives for protection against corrosion

stabilizers

solvents, such as water, alcohols, glycols, glycol ethers, etc. (forexample ethanol, propanols, 1,2-propylene glycol, triethylene glycol,1-methoxypropan-2-ol, butyl diglycol, phenoxyethanol, phenoxypropanols)

The compositions according to the invention can comprise aqueous and/ororganic phases. They can be present in liquid, liquid-viscous orpaste-like form. They can be present in the form of a concentrate or aready-to-use solution.

The content of carbamic acid derivative(s) is generally greater than 1%by weight, preferably greater than 5% by weight and in particulargreater than 10% by weight.

The content of methylenebisoxazolidine derivative(s) is generally notgreater than 99% by weight, preferably not greater than 95% by weightand in particular not greater than 90% by weight.

The compositions according to the invention may also comprise onlycarbamic acid derivative(s) and methylenebisoxazolidine derivative(s),without other substances being added.

The compositions according to the invention are generally prepared bymethods known in the art. In general, it is sufficient to simply mix thecomponents at room temperature or with heating, for example to up to100° C., in combination with work-up steps such as filtration and thelike, to obtain the compositions according to the invention.

The preparations obtained according to the invention can be incorporatedadvantageously into industrial products, such as liquid microbicidalproducts and water-soluble microbicidal products, and be used in cropprotection or in the treatment of seed (plant hygiene). Furthermore,they can be incorporated into industrial preservatives havingmicrobicidal activity, container preservatives, cutting fluid additives,fuel additives and other industrial preservatives. They can also beemployed in disinfectants, in particular in low-foam disinfectantshaving microbicidal activity. They can also be used in compositions forcontrolling pruning wound parasites on plants, compositions for treatingplant pruning wounds, disinfectants for applications where colonizationby fungi is very likely, film preservatives for external and inparticular internal applications and wood protection compositions.

The incorporation of the compositions according to the invention intoindustrial products, for example those mentioned above, can be carriedout by adding the previously finished composition. Alternatively, theaddition can be carried out by incorporating the components of thecompositions according to the invention separately at the same time, orelse at different times, into the industrial products.

The concentrations used here are generally greater than 0.01% by weight,preferably greater than 0.05% by weight and in particular greater than0.10% by weight, based on the weight of the industrial product.

DETAILED DESCRIPTION OF THE INVENTION EXAMPLES Example 1 PreparationsBased on Fungicides or Biocides and Specific N-formals

TABLE 1 Test materials and test methods Fungi-algae test: Test materialPure acrylate house paint Test method Fungicidal finish (SM 022)Algistatic finish (SM 023) Test germs algae Chlorella fusca (CF) Testgerms fungi Aspergillus niger (AN) Penicillium funiculosum (PF)Alternaria alternata (AL) Test substances: Blank House paint withoutpreservative DF 27 Parmetol DF 27* (as standard) 431/043 90% by weightof Mar 71 + 10% by weight of carbendazim Mar 713,3′-Methylenebis(5-methyloxazolidine) 426/160 9% by weight ofcarbendazim dispersion (content of active compound based on thedispersion) *Parmetol DF 27 = aqueous dispersion of Irgarol 1051(2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine),carbendazim and zinc pyrithion

Procedure:

In separate batches, the test concentrations of the activecompounds/products were incorporated into the house paint, and thefungicidal and/or algistatic finish was determined using the stated testmethods. Incorporation and testing were carried out according to themethods SM 022 and SM 023 below.

Test Method SM-022 Determination of the Resistance to Fungal Attack

This laboratory method was used to determine the resistance of housecoatings to fungal attack. For the method, house coatings onstandardized paper were used as test substrate, and Aspergillus niger(ATCC 6275) and Penicillium funiculosum (ATCC 36839) were used as testfungi. The experiments were carried out in Petri dishes on dextrosenutrient medium.

Sample Preparation:

50 g of the material to be finished were, in separate batches, mixedwith various concentrations of the fungicide to be examined andhomogenized for 3-5 min using a basket stirrer.

Preparation of the Test Objects:

Paper carrier materials having the dimensions 90×270 mm (Schleicher &Schüll No. 2589 B/X 24078) were coated with the test material. The paintand/or render samples were coated to a wet-layer thickness of 250 μm byknife coating. The knife had an opening of a width of at least 6.5 cm.In the case of renders, the layer thickness depended, as in practice, onthe particle size. The coated carrier materials, hereinbelow referred toas test bodies, were subsequently dried in a horizontal position forfive days.

Pretreatment of the Test Bodies:

The test bodies were watered in running tap water of 15±5° C. and a flowrate of 1 l/min for 72 hours and subsequently dried for two days. Thecross section of the container for the watering in the direction of flowwas 1000±500 cm².

From the pretreated test bodies, sample bodies having a diameter of 5 cmwere punched out and sterilized in a Co⁶⁰ source using at least 10 kGy.

Test Protocol:

Inoculation and Incubation:

The Sabouraud dextrose agar, which had solidified in the Petri dish, wasinoculated with 0.2 ml of spore suspension (10⁷ spores/ml) and platedout using a sterile Drigalski spatula or an offset sterile glass rod.

The pretreated sample bodies were then evenly placed onto the inoculatedsurface of the nutrient medium using a pair of tweezers, making surethat the entire surface of the sample body was in contact with thesurface of the nutrient medium. The sample was subsequently incubated at30±2° C. for three weeks. For other test germs, the incubationtemperature had to be adapted to achieve optimum growth.

Evaluation:

After one, two and three weeks, the sample bodies were examined forfungal growth. Evaluation was carried out visually or—if this wasrequired to exclude foreign infections—using a magnifying glass. If theextent of the colonization by foreign organisms observed considerablyinterfered with the evaluation, the experiment could not be evaluatedand was repeated. The evaluation of the samples was based on thefollowing evaluation scale:

00—entire plate free from colonization*

0—zone formation (no colonization around the sample)*

(0)—fungal colonization up to the sample*

1—only the sample edge is colonized*

2—the sample is colonized from the edge inwards (less than 25%)

3—the sample surface is colonized by individual colonies (25-75%)

4—the sample surface is colonized extensively (75% and more, but not theentire surface)

5—the sample surface is colonized completely (100%) *Note: Samplesevaluated as 00, 0, (0) and 1 can be referred to as “being effectivelyfinished against fungal growth”.

Test Method SM-023 Determination of the Resistance to Colonization byAlgae

This laboratory method was employed for determining the resistance ofhouse coatings to colonization by algae. For this method, house coatingson standardized paper are used as test substrate and Chlorella fusca isused as test alga. It is furthermore possible to use pure cultures ofother algae species of practical relevance.

The experiments were carried out in Petri dishes on agar nutrient media.

Sample Preparation:

50 g of the material to be finished were, in separate batches, mixedwith various concentrations of the algicide to be examined andhomogenized for 3-5 min using a basket stirrer.

Preparation of the Test Objects:

Paper carrier materials having the dimensions 90×270 mm (Schleicher &Schüll No. 2589 B/X 24078) were coated with the test material. The paintand/or render samples were coated to a wet-layer thickness of 250 μm byknife coating. The knife had an opening of a width of at least 6.5 cm.In the case of renders, the layer thickness depends, as in practice, onthe particle size. The coated carrier materials, hereinbelow referred toas test bodies, were subsequently dried in a horizontal position forfive days.

Pretreatment of the Test Bodies:

The test bodies were watered in running tap water of 15±5° C. and a flowrate of 1 l/min for 72 hours and subsequently dried for two days. Thecross section of the container for the watering in the direction of flowwas 1000±500 cm².

From the pretreated test bodies, three sample bodies having a diameterof 5 cm were punched out and sterilized in a Co⁶⁰ source using at least10 kGy.

Test Protocol:

Inoculation and Incubation:

Aseptically, the samples were placed onto the algae nutrient media, andthe centre of the sample was inoculated with 5 ml of each algaesuspension.

The mixture of the algae suspensions was spread on the surface using aDrigalski spatula or an offset sterile glass rod.

During the growth phase at 22±20° C., the coated samples in the Petridishes were irradiated with light of an intensity of about 1000 Lux(customary fluorescent tubes, type D 67 daylight). A cycle of in eachcase 12 hours of irradiation and 12 hours of storage in the dark wasused.

Evaluation:

The colonization of the samples by algae was examined and evaluatedafter two weeks. Evaluation was carried out visually. The evaluation ofthe samples was based on the following evaluation scale:

Group 1:

No growth of algae on the test bodies

Formation of an inhibitory zone or growth of algae on the nutrientmedium up to the edge of the test bodies

Paints of this group can be characterized by the term “effectivelyfinished against colonization by algae”.

Group 2:

Visible colonization of the test body by algae

− = no growth + = some growth ++ = moderate growth +++ = strong growth

The results are shown in Tables 2 and 3 below.

TABLE 2 Results of the tests from Table 1 on the algicidal activity UseInhibitory Surface Test substances: concentration zone in mmcolonization Remarks Algistatic finish: without stress due to leachingBlank 0 +++ None Parmetol DF 27 3.0% by weight >18 − Withoutdiscoloration 2.0% by weight >18 − Without discoloration 1.0% byweight >18 − Without discoloration 431/043 2.0% by weight >18 − Withoutdiscoloration 1.0% by weight >18 − Without discoloration 0.5% byweight >18 − Without discoloration Mar 71 2.0% by weight >18 − Withoutdiscoloration* 1.0% by weight >18 − Without discoloration 0.5% by weight12 − Without discoloration 426/160 2.22% by weight 0 +++ Withoutdiscoloration 1.11% by weight 0 +++ Without discoloration 0.55% byweight 0 +++ Without discoloration Algistatic finish: stress due to 72hours leaching Blank 0 +++ None Parmetol DF 27 3.0% by weight >18 −Without discoloration 2.0% by weight >18 − Without discoloration 1.0% byweight >18 − Without discoloration 431/043 2.0% by weight 0 ++ Withoutdiscoloration 1.0% by weight 0 ++ Without discoloration 0.5% by weight 0++ Without discoloration Mar 71 2.0% by weight 0 +++ Withoutdiscoloration 1.0% by weight 0 ++ Without discoloration* 0.5% by weight0 ++ Without discoloration 426/160 2.22% by weight 0 +++ Withoutdiscoloration 1.11% by weight 0 +++ Without discoloration 0.55% byweight 0 +++ Without discoloration Key: *Some lumps are formed in thehouse paint − = no growth + = some growth ++ = moderate growth +++ =strong growth

TABLE 3 Results of the tests from Table 1 on the fungicidal activityTest germs Fungicidal finish: Use conc. AN PF Without stress due toleaching Time (weeks) 1 2 1 2 Blank 5 5 5 5 Parmetol DF 27 3.0% byweight 0 0 0 0 2.0% by weight 0 0 0 0 1.0% by weight 0 (0) 0 0 431/0432.0% by weight 0 1 00  00  1.0% by weight 1 2 0 0 0.5% by weight 1 2 0 0Mar 71 2.0% by weight 5 5 3 4 1.0% by weight 5 5 5 5 0.5% by weight 5 55 5 426/160 2.22% by weight 0 0 0 0 1.11% by weight (0) (0) 0 0 0.55% byweight (0) (0) 0 0 Stress due to 72 hours leaching Time (week) 1 2 1 2Blank 5 5 5 5 Parmetol DF 27 3.0% by weight (0) (0) 0 0 2.0% by weight(0) (0) 0 0 1.0% by weight 1 1 0 0 431/043 2.0% by weight 5 5 5 5 1.0%by weight 5 5 5 5 0.5% by weight 5 5 5 5 Mar 71 2.0% by weight 5 5 5 51.0% by weight 5 5 5 5 0.5% by weight 5 5 5 5 426/160 2.22% by weight 11 0 0 1.11% by weight 1 1 0 0 0.55% by weight 1 1 0 0 Key: 00 = entireplate free from colonization 0 = zone formation (no colonization aroundthe sample) (0) = fungal colonization up to the sample 1 = only thesample edge is colonized 2 = the sample is colonized from the edgeinwards (less than 25%) 3 = the sample surface is colonized byindividual colonies (25%-75%) 4 = the sample surface is colonizedextensively (75% and more, but not the entire surface) 5 = the samplesurface is colonized completely (100%)

Results:

Discoloration:

Use concentrations of 2% by weight of 431/043 or Mar 71 or carbendazimdid not result in any discoloration of the finished paint samples. A useconcentration of 2% by weight of Mar 71 resulted in the formation ofsome lumps in the paint sample.

Algicidal Action:

Without stress due to leaching, 431/043 and Mar 71 (use concentrationfrom 0.5 to 2% by weight) showed good algicidal activity, the algicidalactivity of 431/043 being better than that of Mar 71 on its own. Withstress due to leaching, Mar 71 and 431/043 showed little algicidalaction in practice; however, 431/043 effected a reduction of growth onthe surface.

Without and with stress due to leaching, carbendazim showed, at anactive compound concentration of 0.2% by weight (active compoundconcentration based on the total composition of house paint and testsubstance), no algicidal action in the algae test.

Fungicidal Action:

At a use concentration of from 0.5 to 2% by weight, 431/043 showed,without stress due to leaching, a sufficiently high activity against thetest germs AN and PF. Mar 71 showed no fungicidal activity in practice.

Summary:

Without stress due to leaching, 431/043 showed good algicidal andsatisfactory fungicidal action against the test germs AN and PF. Withstress due to leaching, the activity against algae and fungi wasreduced.

EXAMPLE 2 Activity in Industrial Products

TABLE 4 Test methods and samples used Boko test: Test products: 431/044A Mar 71 431/043 10% by weight of carbendazim + 90% by weight of Mar 71

Sample 431/043 was prepared by maintaining 10% by weight of carbendazimand 90% by weight of Mar 71, based on the resulting composition, at80-85° C. for 5 h. The mixture was subsequently filtered through a Seitzfilter, giving a brown-yellow clear solution. The Boko test was carriedout as described below:

In separate batches, in each case 100 ml of the water-diluted cuttingfluid to be preserved were admixed with various concentrations of thepreservatives to be examined. The growth control used was in each casean unpreserved sample.

Two days after the incorporation of the preservatives, the test batcheswere infected for the first time using 1 ml of an inoculating solution.The inoculating solution used was a suspension of the germs listed below(cultivated on nutrient media and then adapted to water-diluted cuttingfluids). The inoculating solution had a titre of at least 10⁷ germs/ml.

Bacteria Escherichia coli ATCC 11229 Klebsiella pneumoniae ATCC 4352Pseudomonas aeruginosa ATCC 15442 Yeasts Candida albicans ATCC 10231Rhodotorula mucilaginosa (rubra) DSM 70403 Fungi Fusarium oxyspocum ATCC62318

The test batches were subsequently inoculated two times a week andplated onto agar plates two times per week, the first smear beingcarried out immediately prior to the new inoculation. The microbialgrowth on the smears was assessed after incubation at 25° C. for threedays. To be on the safe side, negative smears were observed for anothertwo days and then reassessed. The preservative effect of the individualproduct concentrations was assessed in a semiquantitative method by thecolonization of the individual smears using the classification from −to + to +++. Growth was differentiated according to bacteria, yeasts andmoulds.

− = no colonization + = some colonization ++ = moderate colonization +++= strong colonization

The test was usually carried out for twelve inoculation cycles orinterrupted after repeated +++ growth.

Test Conditions:

The cutting fluids Shell Dromus BX or Almasol EP from Castrol orRondocor Kompakt from Consulta were examined as 4% strength by weightemulsions in tap water from the city of Norderstedt. Inoculation wascarried out using a suspension of bacteria or fungi or a mixedsuspension of bacteria and fungi.

TABLE 5 Results of the Boko test according to Table 4 Number ofinoculation cycles passed on inoculation with: Bacteria Fungi Mixed Useconcentration suspension suspension suspension Cutting fluid ShellDromus BX, based on mineral oil 431/044 A Blank 0 0 0 0.15% byweight >12 >12 >12 0.10% by weight >12 >12 11 0.05% by weight >12 >12 4431/043 0.15% by weight >12 >12 >12 0.10% by weight >12 >12 >12 0.05% byweight >12 >12 0 Cutting fluid Almasol EP, based on mineral oil,comprising amine 431/044 A Blank 0 0 0 0.15% by weight >12 >12 11 0.10%by weight >12 >12 >12 0.05% by weight >12 >12 11 431/043 0.15% byweight >12 >12 >12 0.10% by weight >12 >12 >12 0.05% by weight >12 >1211 Cutting fluid Rondocor Kompakt, comprising mineral oil 431/044 ABlank 7 5 0 0.15% by weight >12 >12 >12 0.10% by weight >12 >12 >120.05% by weight >12 >12 >12 431/043 0.15% by weight >12 >12 >12 0.10% byweight >12 >12 >12 0.05% by weight >12 >12 >12

Results:

In cutting fluids based on mineral oil (Shell Dromus BX and Almasol EP,comprising amine), Mar 71 and the preparation of Mar 71 and carbendazim(90+10% by weight) were, in the concentration range examined, similarlyeffective against bacteria and fungi and against a mixed culture ofbacteria and fungi. The advantages of the combination of Mar 71 andcarbendazim became evident.

EXAMPLE 3 Preparations of Mar 71, Carbendazim and Other Biocides

With stirring, 800 g of Mar 71 and 100 g of carbendazim were heated at78-80° C. for 9 hours. The slightly turbid product was filtered(presolution 437/097) and in each case admixed with 10% by weight of thefollowing biocides (all data in per cent by weight, based on the totalcomposition).

A B C D Mar 71 10 Kathon 893¹⁾ 10 IPBC¹⁾ 10 Na pyrion (40% by weight) 10Presolution 437/097 90 90 90 90 ¹⁾45% by weight of N-octylisothiazolonein 1,2-propylene glycol ²⁾iodopropynyl butylcarbamate

After filtration through a Seitz filter, all solutions were clear andlight-brown.

EXAMPLE 4 Preparations Based on Mar 71 and Carbendasulf

A B C D E F Mar 71 100 80 60 40 20 Carbendasulf sol.* — 20 40 60 80 100*10.5% by weight of carbendasulf in 1,2-propylene glycol

After mixing the starting materials, clear, colourless to yellowishsolutions are obtained.

EXAMPLE 5 Activity of Compositions of Mar 71 and Carbendazim

Preparations:

G 5620  1% by weight carbendazim + 99% by weight Mar 71 G 5621  2% byweight carbendazim + 98% by weight Mar 71 G 5622  5% by weightcarbendazim + 95% by weight Mar 71 G 5623 10% by weight carbendazim +90% by weight Mar 71 G 5624 Mar 71

Solutions of in each case 2% strength by weight in fully deionized waterwere examined against selected bacteria and/or yeasts and/or fungiand/or algae using the serial dilution test according to DGHM [GermanSociety for Hygiene and Microbiology].

MIC values of the aqueous 2% by weight strength solutions:

PS EC KP CA RM FO PF AN AL CF G 5620 6.25 6.25 6.25 >6.25 1.56 0.78 0.781.56 6.25 0.78 G 5621 6.25 6.25 6.25 >6.25 3.12 0.19 0.19 0.39 6.25 0.39G 5622 6.25 6.25 6.25 >6.25 1.56 0.09 0.09 0.39 6.25 0.39 G 5623 6.256.25 6.25 >6.25 6.25 0.09 0.09 0.19 6.25 0.39 G 5624 6.25 6.253.12 >6.25 3.12 1.56 1.56 6.25 6.25 0.39

Key to Microorganisms:

Bacteria: PS = Pseudomonas aeruginosa EC = E. coli KP = Klebs.pneumoniae Yeasts: CA = Cand. albicans RM = Rhodotorula mucilaginosaFungi: FO = Fusarium oxysporum AN = Asperg. niger PF = Penicilliumfuniculosum AL = Alternaria alternata Algae: CF = Chlorella fusca

The emboldened MIC values denote preparations which were more effectivethan Mar 71. In particular in the case of some yeasts and fungi, thepreparations according to the invention were considerably more effectivethan Mar 71 on its own.

What is claimed is:
 1. A stable microbicidal composition, consistingessentially of 3,3′-methylenebis-(5 methyloxa-zolidine) and derivates of1H-benzimidazol-2-ylcarbamic acid selected from the group consisting ofmethyl 1H-benzimdazol-2-ylcarbamate or its salts, and methyl1-(butylcarbamoyl) benzimidazol-2-ylcarbamate and optionally additives,auxiliaries, and microbicidally active compounds selected from the groupconsisting of N-formals and O-formals.
 2. The composition according toclaim 1, wherein the composition has a pH of up to
 12. 3. Thecomposition according to claim 2, wherein the composition has a pH of upto
 10. 4. The composition according to claim 1, wherein additives,auxiliaries, and microbicidally active compounds selected from the groupconsisting of N-formals and O-formals are present.
 5. The compositionaccording to claim 1, wherein the composition is in aqueous and/ororganic phases.
 6. The composition according to claim 1, wherein thecomposition is present in the form of a liquid, liquid-viscous, orpaste.
 7. The composition according to claim 1, wherein the compositionis present as a concentrate.
 8. The composition according to claim 1,wherein the composition is present in the form of a ready-to-usesolution.
 9. The composition according to claim 1, wherein the contentof carbamic acid derivative is greater than 5% by weight.
 10. Thecomposition according to claim 9, wherein the content of carbamic acidderivative is greater than 10% by weight.
 11. The composition accordingto claim 1, wherein the content of methylenebisoxazolildine derivativeis not greater than 99% by weight.
 12. The composition according toclaim 11, wherein the content of methylenebisoxazolildine derivative isnot greater than 90% by weight.
 13. Method of adding a compositionaccording to claim 1, an industrial product selected from the groupconsisting of crop protection compositions, compositions for thetreatment of seed, industrial preservatives having microbicidalactivity, cutting fluid additives, fuel additives, disinfectants,compositions for treating plant pruning wounds, film preservatives forexternal and internal applications, and wood protection compositions,the method comprising adding the composition in concentrations ofgreater than 0.01% by weight based on the weight of the industrialproduct.
 14. The method according to claim 13, wherein the compositionis added in concentrations of greater than 0.10% by weight based on theweight of the industrial product.
 15. The method according to claim 13,wherein the components of the composition are incorporated into theindustrial product separately at different times.
 16. Method ofincreasing the solubility of derivatives of 1H-benzimidazol-2-ylcarbamicacid selected from the group consisting of methyl1H-benzimdatol-2-ylcarbamate or its salts and methyl 1-(butylcarbamoyl)benzimidazol in a liquid preparation, consisting essentially of addingto said liquid preparation an effective amount of 3,3′-methylenebis (5methylox-azolidine) and optionally additives, auxiliaries, andmicrobicidally active compounds selected from the group consisting ofN-formals and O-formals.
 17. The method according to claim 16, whereinadditives, auxiliaries, and microbicidally active compounds selectedfrom the group consisting of N-formals and O-formals are present. 18.The method according to claim 16, wherein the liquid preparation is inaqueous and/or organic liquid phases.
 19. The method according to claim16, wherein the liquid preparation has a pH of up to
 12. 20. The methodaccording to claim 19, wherein the liquid preparation has a pH of up to10.
 21. The method according to claim 16, wherein the content ofcarbamic acid derivative in the liquid preparation is greater than 1% byweight.
 22. The method according to claim 21, wherein the content ofcarbamic acid derivative in the liquid preparation is greater than 10%.23. The method according to claim 16, wherein the content ofmethylenebisoxazolildine derivative in the liquid preparation is notgreater than 99% by weight.
 24. The method according to claim 23,wherein the content of methylenebisoxazolildine derivative in the liquidpreparation is not greater than 90% by weight.
 25. The method accordingto claim 16, wherein the liquid preparation is present in the form of aconcentrate or a ready-to-use solution.